Photomodulation of DNA-Templated Supramolecular Assemblies (original) (raw)
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From Interaction to Function in DNA‐Templated Supramolecular Self‐Assemblies
ChemistryOpen, 2020
DNA-templated self-assembly represents a rich and growing subset of supramolecular chemistry where functional self-assemblies are programmed in a versatile manner using nucleic acids as readily-available and readily-tunable templates. In this review, we summarize the different DNA recognition modes and the basic supramolecular interactions at play in this context. We discuss the recent results that report the DNAtemplated self-assembly of small molecules into complex yet precise nanoarrays, going from 1D to 3D architectures. Finally, we show their emerging functions as photonic/electronic nanowires, sensors, gene delivery vectors, and supramolecular catalysts, and their growing applications in a wide range of area from materials to biological sciences.
Fluorescent Dynamic Covalent Polymers for DNA Complexation and Templated Assembly
Molecules
Dynamic covalent polymers (DCPs) offer opportunities as adaptive materials of particular interest for targeting, sensing and delivery of biological molecules. In this view, combining cationic units and fluorescent units along DCP chains is attractive for achieving optical probes for the recognition and delivery of nucleic acids. Here, we report on the design of acylhydrazone-based DCPs combining cationic arginine units with π-conjugated fluorescent moieties based on thiophene-ethynyl-fluorene cores. Two types of fluorescent building blocks bearing neutral or cationic side groups on the fluorene moiety are considered in order to assess the role of the number of cationic units on complexation with DNA. The (chir)optical properties of the building blocks, the DCPs, and their complexes with several types of DNA are explored, providing details on the formation of supramolecular complexes and on their stability in aqueous solutions. The DNA-templated formation of DCPs is demonstrated, whi...
Chemistry (Weinheim an der Bergstrasse, Germany), 2017
We provide here a proof-of-principle that coordination chemistry drives the in situ self-assembly of an inactive ligand into a multivalent cluster capable of effectively complexing DNA. We show that metal coordination and scavenging can be used to switch the multivalency of the system. Thereby, controlled DNA complexation and decomplexation could be achieved.
DNA as supramolecular scaffold for functional molecules: progress in DNA nanotechnology
Chemical Society Reviews, 2010
Oligonucleotides have recently gained increased attraction as a supramolecular scaffold for the design and synthesis of functional molecules on the nanometre scale. This tutorial review focuses on the recent progress in this highly active field of research with an emphasis on covalent modifications of DNA; non-covalent interactions of DNA with molecules such as groove binders or intercalators are not part of this review. Both terminal and internal modifications are covered, and the various points of attachment (nucleobase, sugar moiety or phosphodiester backbone) are compared. Using selected examples of the recent literature, the diversity of the functionalities that have been incorporated into DNA strands is discussed.
Journal of the American Chemical Society
Self-assembled nucleobases, such as G-quartets or quadruplexes, have numerous applications but light-responsive structures are limited to small, non-crystalline motifs. In addition, the assembly of the widely exploited azobenzene photochromic compounds can produce fluorescent crystals of extended dimensions but at the prize of sacrificing their photoswitchability. Here we overcome inherent limitations of self-assembly with a new concept of supramolecular co-assembly leading in fine to materials with unprecedented properties. We show that the co-assembly of guanosine monophosphate (GMP) with an azobenzene-containing DNA intercalator produce supramolecular crystals arranged through a combination of π-π, electrostatic and hydrogen bond interactions. The resulting crystals are 100 µm long, pH-sensitive, fluorescent and can be photoreversibly disassembled/reassembled upon UV/blue irradiation. This allows us to perform operations such as dynamic photocontrol of a single crystal growth, light-gated permeability in membrane-like materials and photoswitchable fluorescence. We believe this concept critically expands the breadth of multifunctional materials attainable by self-assembly.
Bioconjugate Chemistry, 2008
Here, we present the synthesis, photochemical, and DNA binding properties of three photoisomerizable azobenzene-distamycin conjugates in which two distamycin units were linked via electron-rich alkoxy or electronwithdrawing carboxamido moieties with the azobenzene core. Like parent distamycin A, these molecules also demonstrated AT-specific DNA binding. Duplex DNA binding abilities of these conjugates were found to depend upon the nature and length of the spacer, the location of protonatable residues, and the isomeric state of the conjugate. The changes in the duplex DNA binding efficiency of the individual conjugates in the dark and with their respective photoirradiated forms were examined by circular dichroism, thermal denaturation of DNA, and Hoechst displacement assay with poly[d(A-T).d(T-A)] DNA in 150 mM NaCl buffer. Computational structural analyses of the uncomplexed ligands using ab initio HF and MP2 theory and molecular docking studies involving the conjugates with duplex d[(GC(AT) 10 CG)] 2 DNA were performed to rationalize the nature of binding of these conjugates.
International Journal of Molecular Sciences, 2015
DNA-templated self-assembly is an emerging strategy for generating functional supramolecular systems, which requires the identification of potent multi-point binding ligands. In this line, we recently showed that bis-functionalized guanidinium compounds can interact with ssDNA and generate a supramolecular complex through the recognition of the phosphodiester backbone of DNA. In order to probe the importance of secondary interactions and to identify side groups that stabilize these DNA-templated self-assemblies, we report herein the implementation of a dynamic combinatorial approach. We used an in situ fragment assembly process based on reductive amination and tested various side groups, including amino acids. The results reveal that aromatic and cationic side groups participate in secondary supramolecular interactions that stabilize the complexes formed with ssDNA.